AU2006201088B2 - Waxy grain products and process for producing same - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): KELLOGG COMPANY THE UNITED STATES OF AMERICA REPRESENTED BY THE SECRETARY OF AGRICULTURE.

Invention Title: WAXY GRAIN PRODUCTS AND PROCESS FOR PRODUCING SAME The following statement is a full description of this invention, including the best method of performing it known to me/us: WO 01/49132 PCT/US01/00027 WAXY GRAIN PRODUCTS

AND

PROCESSES FOR PRODUCING SAME FIELD OF THE INVENTION This invention relates to a palatable, cooked, storage stable, buoyant food oo product prepared from waxy grains, particularly waxy barleys. Generally, waxy 00 0 5 grains contain no more than 10% amylose. The cooked, waxy grain is storage stable, Se.g., it can be stored in tightly closed or air tight containers for prolonged periods of NO time without additives that inhibit the development of rancidity and yet the cooked C,1 waxy grains of this invention do not become rancid. Preferably, the waxy grain is a waxy, hulless barley and may contain about 16% total dietary fiber about 5% to about 7% P-glucan and total tocopherol of about at least 40 ug/g grain dry weight. The processes for preparing the palatable, cooked, storage stable, buoyant waxy grains of this invention are also described.

BACKGROUND OF THE INVENTION Grains are a valuable source of micro and macro nutrients, carbohydrates, proteins, vitamins, antioxidants and both soluble and insoluble fiber, but raw grain, amaranth, barley, maize, oat, rice, sorghum and wheat, is generally unpalatable and not easily digested. Thus grain is usually processed by cooking to a form that is 'more easily digested and also possesses pleasing organoleptic properties of appearance, aroma, taste and texture. The nutritional value and organoleptic properties of the processed grain and their ability to be stored for long periods of time depend on a combination of factors, on the type of grain that is processed, e.g., whether the grain possesses high levels of fiber and antioxidants, the levels oflipase and peroxidase in the processed grain, the types and amounts of starch in the processed grain, amylopectin or amylose, and the steps used to process the grain.

Grains are a good source of fiber and a diet high in fiber has been associated WO 01/49132 PCT/US01/00027 0 with various health benefits, lowering cholesterol, modulating blood sugar levels, which is an important consideration for persons with diabetes, and reducing the risk of colin cancer (LaBell, Healthy Barley Foods Multiply, 87 (Nov. 1997). High serum cholesterol is a recognized risk factor for heart disease and is reversible by diet in a majority of cases (Connor and Connor, "The Dietary Prevention and Treatment of 00 Coronary Heart Disease." In: Coronary Heart Disease, W.E. Connor and J.D.

Bristow, Eds. J.B. Lippincott, Philadelphia, 1984). Three factors modified in a diet to reduce cholesterol include: reducing total fat, increasing the ratio of polyunsaturated to saturated fatty acids, and consuming soluble dietary fiber. Dietary to fiber consists of a mixture of components which vary in degree of solubility in water and soluble fibers are well-documented as having beneficial hypocholesterolemic benefits (Newman et al., Cereal Foods World, 34(10)883-886 (1989)). Components that are considered generally soluble in water include pectin, gums, and mixed linked (1-4)--glucans, such as, the 0-glucans found in the oat bran and in endosperm cell walls of barley. About 70% of the barley endosperm cell walls are 3glucans. However, the hypocholesterolemic effects of isolated P-glucans and the hypocholesterolemic effects of certain milling fractions of grain are not the same as those of a grain product, which contains intact endosperm cell walls (Newman et al., "The Hypocholesterolemic Function of Barley p-Glucans," Cereal Food World, 34(10):883-884, 1989).

Grains also provide antioxidants, which are thought to be protective against cardiovascular disease and various cancers. Tocopherols, Vitamin E, is a potent antioxidant. In its natural food state, Vitamin E is actually a family of several different tocopherols, alpha, beta, epsilon, and gamma. Animal and in vitro studies indicate that Vitamin E supplementation reduces the risk of chemical- and radiation-induced cancers.

The starch makeup of grains can affect the organoleptic characteristics of processed grains. Grains contain a combination of two kinds of starch, amylose and WO 01/49132 PCT/US01/00027 O amylopectin. Amylose is a straight chain glucose polymer having a-1,4 linkages.

Amylopectin is a branched chain glucose polymer with 1-6 linkages at the branching Spoints. Grains designated "waxy" or "non-waxy" differ in their content of amylose t and amylopectin starches. Generally, grains having 10% or less amylose are designated "waxy." Waxy varieties exist for barley, maize, oat, rice, sorghum, and 00 wheat, and some have been used previously in a variety of methods to produce palatable and digestible food products. Unlike raw grains, which may be stored for long periods of time without deteriorating, provided the grain is kept dry, processed grains and products comprising the processed grains are often subject to mold and 1O bacterial growth as well as oxidative and enzymatic degradation. Thus many processed grains, and food products comprising the processed grains, are not shelf stable, they cannot be stored for long periods without becoming rancid and losing their pleasing appearance, aroma, taste and texture, unless they are treated with preservatives to inhibit the development of rancidity.

United States patent 2,526,792 to Aldeman discloses the preparation of a pearled waxy barley-based cooked and puffed product. The method described does not include steps that would make the product shelf stable for prolonged periods of time.

United States Patent 2,930,697 to Miller discloses a process wherein grain, e.g., wheat, oat, sorghum and rye is soaked to increase its moisture level, flattened to break the epidermis and endosperm and then cooked with steam or with water to uniformly gelatinize the starch. Miller does not disclose the use of waxy grains.

United States patent 4,603,055 to Karowski et al. is directed to the production of cereal flakes that are thicker than normal toasted flakes and have a high flake integrity that withstands packaging, shipping and dehydration cooking. Karowski et al. produce a multiple grain based flaked cereal from a plurality of grain types that are cut into pieces and then steamed and tempered for 15-20 minutes but the grains are only partially gelatinized prior to rolling into a flake.

WO 01/49132 PCT/US01/00027 United States patent 5,391,388 to Lewis et al. discloses the preparation of a cI waxy barley-based porridge-like breakfast cereal wherein less than 30% of the starch Sis gelatinized. This is a partially gelatinized, partially cooked quick cooking hot tr cereal. The patent also discloses a non-crispy cold breakfast cereal food.

United States patent 5,360,619 to Alexander relates to cereal foods ingredients 00 from waxy barley. The cereal food products of this patent are not gelatinized 00 0throughout and the grain is pearled and thus lacks the outer parts of the grain. The c, outer part of the grain is a source of fiber and therefore by pearling, the grain reduces 0 the proportion of beneficial fiber in the cereal food ingredients of this patent.

European patent application 0 338 239 to inventors Short and Wilkinson, describes a method for producing a microwaveable half product and a puffed food product from flour of one or more grains, one of which being a whole ground waxy maize. While the process disclosed therein fully gelatinizes the starch, the product is prepared from a dough and the products are not storage stable. They rapidly undergo enzymatic and oxidative rancidity resulting in a product having a taste, odor and texture that is not acceptable to consumers.

International application WO 96/19117 (inventor Lewis) discloses a method that includes a step that reportedly fully gelatinizes waxy grains, either whole or subdivided. However, the product cannot be stored for prolonged periods without becoming rancid without additives to inhibit the development of rancidity.

U.S. patent 4,737,37 1 discloses a treatment for protecting grain from enzymatic deterioration by inactivation oflipolytic and oxidative enzymes prior to milling into a shelf stable high fat flour. The grain is soaked for a prolonged period to raise the moisture content to 13-17%, then quickly heated, cooled and stored or milled into a flour. The patent does not disclose fully gelatinizing the grains or the use of waxy grains.

U.S. Patent 4,413,018 to Webster et al. discloses a process for imparting shelf stability to oat groats wherein the groats are heated for a time and temperature WO 01/49132 PCT/US01/00027 0 sufficiently intense to inactivate the enzymes with causing the oxidative reaction I process to go forward. The oats are treated to reduce the moisture level by heating over a period of 1-2 hours, then slowly cooled and thereafter steamed or boiled for t¢ 10 minutes. This patent also does not disclose waxy grains.

While heating may seem a straightforward alternative to deactivating enzymes, 00 U.S. Patent 6,156,365 to Liwszyc discloses that some heat treatments while capable of inhibiting enzymes, actually accelerate the oxidative rancidity. Liwszyc discloses Ci a process for preparing a fully and uniformly gelatinized hulled non-waxy oat Scomprising adding water to the hulled oats and cooking the oats for a time and at a to temperature to fully gelatinize the oats. This patent deactivates active enzymes in oat bran by steaming hulled oats in the presence of heat (100°C, 212°F) for 1 to 3 hours and discloses that further harsh treatment of hulled oats leads to the destruction of antioxidants and shortening the shelf life of the finished product. The flakes produced by the described method are reported to be more water absorbent than traditional oat flakes. This patent does not disclose waxy grains.

The processes described herein are suitable for application to waxy grains that may or may not be pearled but are particularly useful for processing waxy grains that are high in lipases and peroxidases, waxy barleys and waxy wheats. The processes of this invention produce a digestible, palatable, buoyant, waxy grain that is a storage stable, gelatinized throughout, and that is organoleptically acceptable to consumers. In addition to being storage stable, the products prepared from grain that is not pearled also provide the amounts of fiber and P-glucans found in grain as harvested as well as high levels of antioxidants. This is especially true for grains where p-glucans are found in the bran of the grain, in oat bran.

SUMMARY OF THE INVENTION This invention relates to a palatable, easily digested, storage stable, food product produced from waxy grains, barley, maize, rice or oat, particularly waxy WO 01/49132 PCT/US01/00027

\D

barley. Various grains are available as waxy varieties, for example, barley, maize, CI rice, sorghum and wheat. Grains are an valuable source of fiber, 3-glucans in the endosperm walls of barley and the bran of oat) and antioxidants. In view of the tIt desirable characteristics of waxy grains and the advances in plant technology it is likely that other grains, a waxy oat, will be bred, by either traditional breeding 00 techniques or through genetic modifications using recombinant DNA technology and 00 the processes described herein will be applicable to newly developed waxy grains.

The processes are especially applicable to waxy grains having lipases and peroxidases \0 0 at high levels in the raw state, levels that are about as high or higher than those C 10 in raw non-waxy or waxy wheats, barleys and oats.

The products of this invention display enhanced shelf life, crispness, bowl life and buoyancy as compared to products prepared from non-waxy varieties. Preferably, the uncooked waxy grain has high levels of total and soluble fiber, high levels of 1-glucans, and high levels of antioxidants, tocopherols, and these levels are preserved in the cooked waxy grain of this invention.

Waxy grains generally have no more than 10% amylose and may be selected from wheat, rice, oat, sorghum (millet), maize, and barley. Particularly useful grains are waxy hulless varieties. The hulless gene produces a grain without an adhering hull. Thus it is not necessary to pearl hulless grain to obtain a palatable grain product that is acceptable to consumers. Because it is not necessary to dehull a hulless grain, the resulting product contains essentially the same amount of fiber and P-glucan as is found in the grain as harvested. Thus food products with increased amounts of total dietary fiber as compared to products made from pearled grains, are obtained.

The waxy grain products of this invention have many characteristics desired by consumers. For example, the waxy grain product is storage stable, it can be stored in airtight containers or conventional cereal containers having a liner without becoming rancid, even without the addition of other substances, tocopherols, BHT, etc., to the grain, container or liner, that are commonly used to inhibit the 00 O development of rancid odors and tastes. Thus the product of this invention has e an extended shelf-life. In addition, the finished product of this invention has a unique texture, having a significantly less surface roughness and significantly enhanced buoyancy and crispness as compared to non-waxy products. When exposed to a liquid, such as, milk, the products produced by the methods 00 of this invention display an enhanced crispness and buoyancy, remaining 00 Sbuoyant longer than similar products made with varieties of non-waxy grain.

SThe product produced in one embodiment of this invention is in the form IDof integral whole kernels that are gelatinized throughout. In alternate 0 10 embodiments the product is a flake, a half product or a puffed food product formed from a dough of waxy, grain prepared as described herein. Preferably, the product has high levels of fiber, 13-glucans and tocopherols (vitamin E) provided by the grain itself.

The methods of this invention are suitable for waxy grains that may or may not be pearled. Pearling removes various proportions of the bran from the outer layers of whole grain. For example, a small amount of the bran may be removed, accounting for a loss of only about 1% of the dry weight of the grain, or essentially all the bran may be removed producing a white grain with essentially no brown color from the bran layer. While not all grains require pearling to produce a palatable product, pearled grains produce a product that is preferred by some consumers.

In one aspect, the present invention provides a process for preparing a cooked, buoyant, storage stable, waxy grain comprising: hydrating a waxy grain having no more than 10% amylose to a moisture level of from 11 to 16% and then heating the waxy grain for about 5 to about 15 minutes at about 203°F (95 0 C) to about 230°F (110°C) with moisture to inactivate the lipases and peroxidases, then tempering the waxy grain for about 1 hour to 2 hours; further cooking the tempered waxy grain to fully gelatinize it throughout; and cooling and drying the waxy grain; N:Xelboume\Cases\Patent\47000-47999P47875AU.1\Specis\P47875AU.1 First Amendments.doc 00 -7a- 0 0 Swherein said waxy grain is storage stable for at least six months without r) additives that inhibit development of rancidity.

0 In another aspect, the present invention provides a process for preparing a cooked, buoyant, storage stable, waxy barley comprising: 00 oo hydrating the waxy barley having no more than 10% amylose to a 0 moisture level of from 11 to 16% and then heating the waxy barley for about Sto about 15 minutes at about 203OF (95°C) to about 230 0 F (110°C) with I moisture to inactivate the lipases and peroxidases then tempering the waxy barley for about 1 hour to 2 hours; further cooking the tempered waxy barley to fully gelatinize it throughout; and cooling and drying the waxy barley, wherein said waxy barley is storage stable for at least about six months without additives that inhibit development of rancidity.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of one embodiment of the invention.

Figure 2 is a flow chart of an alternate embodiment of the invention.

Figures 3A and B depict the moisture (3A) and water activity (3B) of a waxy barley flake processed by the methods of this invention at various time during storage for 12 months at 70°F (21.1°C) and 35% relative humidity.

NI\Me boume\Cases\Patoenl47000-47999P47875AU 1\Specs\P47875.AU. 1 First Amendmentsdoc WO 01/49132 PCT/US01/00027 O Figures 4A and B depict the moisture (4A) and water activity (4B) of a waxy CNl barley flake processed by the methods of this invention during storage for 12 weeks at 100°F and 35% relative humidity.

DETAILED DESCRIPTION OF THE INVENTION 00 The methods of this invention use waxy grains having no more than about 00 0 10 amylose. Various grains are available as waxy varieties, for example, barley, rice, sorghum and wheat. In view of the desirable characteristics of waxy grains and Sthe advances in plant technology it is likely that other grains, a waxy oat, will be o 1 bred and the processes described herein will be applicable to newly developed waxy grains. The processes are especially applicable to those having high levels of lipases and peroxidases, levels that are about as high or higher than those in raw nonwaxy or waxy wheats, barleys and oats. Particularly useful waxy grains are those having high levels of fiber, p-glucans or antioxidants, and waxy grains that have a hulless phenotype. Preferred waxy grains are waxy barleys, particularly waxy hulless barleys. Preferably the waxy barley has a high level of fiber, p-glucan and tocopherols vitamin Preferably the waxy barley comprises high levels of fiber, about 14% or more total fiber and high levels of P-glucan, about about 7% p-glucan as well as high amounts oftocopherols, at least about 40 ug/g grain (dry weight).

Plants having a hulless genotype produce kernels without adhering hulls.

Hulless grains in this invention do not require pearling to produce a palatable product.

Pearling removes various amounts of the outer layers of the grain. For example, a small amount of the bran may be removed, accounting for only about 1% of the dry weight of the grain or essentially all the bran may be removed producing a white grain with essentially no brown color from the bran layer. In general, removing the outer grain layers produces a whiter grain with a texture that is desirable by some consumers. However, pearling may produce a nutritionally inferior product because WO 01/49132 PCT/US01/00027 0 the pearled product contains significantly less fiber and P-glucans, in addition to less <C B vitamins, than the grain as harvested. Hulless varieties of grain have been used to prepare food products, but even the hulless varieties have been pearled in some I processes (US patent 5,360,619, supra) to produce the food products.

Most grains, barley, maize; millet, oat, rice, sorghum, and wheat, have 00 varieties that are waxy. Waxy barley varieties include, Waxiro, CDC Candle, 00 Merlin, and HB803, prowashapawana and some that are both waxy and hulless.

Preferably, the waxy grain is a waxy hulless variety. Waxy hulless varieties of barley 0include, CDC Candle, Merlin, and HB803. A preferred barley variety is CDC S 10 Candle.

The methods of this invention are applicable to any waxy grain but are particularly useful for producing digestible, shelf stable grain products from waxy grains that have high levels of lipases and peroxidases in their raw state. High levels of lipases are the levels found in, oats, barleys and wheats. The methods described herein produce a palatable, cooked, storage stable, waxy grain that is readily digested when eaten, and remains shelf stable without the addition of substances that inhibit rancidity. The methods also produce a waxy grain that has an extended bowl life, staying crispy, buoyant and fracturable in milk for at least about 3 minutes; preferably at least about 5 minutes.

Without wishing to be bound by theory, the processes of this invention are thought to inactivate the lipases and peroxidases in the processed grains of this invention wherein the levels oflipase and peroxidase activity being sufficiently low so that the final waxy grain products do not acquire rancid tastes or odors, even after storage for prolonged periods of time in air tight or conventional cereal containers having a liner, without the addition of chemical additives, tocopherols or BHT etc., to inhibit the development of rancid odors and tastes. Preferably, the products are stable for at least 6 months, do not acquire rancid tastes or odors for at least 6 months at ambient temperatures in conventional cereal containers having a liner WO 01/49132 PCT/US01/00027 Ssuch as a Kellogg's Corn Flakes@ or Kellogg's Rice Krispies® box, but wherein

O

NC the liner does not comprise a preservative for inhibiting the development of rancidity.

More preferably, the products are stable for at least 12 months at ambient t temperatures in a conventional cereal box having a liner without the addition of a preservative for inhibiting the development of rancidity.

00 Rancidity may be determined easily by taste or odor, or both taste and odor, 00 oo or by using standard means, gas chromatography, to determine the amount of hexanal produced, by lipid oxidation, in either the headspace of the packaged O grain or in the grain itself. Hexanal accumulates linearly until a certain time, known C lo as the time of break point, wherein the rate of accumulation begins to deviate from linearity and increase exponentially. The break point of rapid hexanal accumulation is close to the time when consumers begin to detect rancidity. Feneley, Accelerated Shelf-Life Testing of a Ready to Eat Cereal, Masters Thesis, Dept. of food Science and Human Nutrition, Michigan State University (1998); Fritsch and Gale, "Hexanal as a measure of rancidity in low fat foods", J. Amer. Oil Chem. Soc. 54:225 (1976).

Furthermore, the product is not only storage stable but also has an enhanced buoyancy. The product of this invention remains buoyant in a liquid, milk, longer than a product prepared from a non-waxy grain, particularly a barley, or a waxy grain, particularly waxy barley, prepared by other methods. The products of this invention have a bowl life, measured by a crispy, fracturable and buoyant character, in milk for at least 3 min. and preferably for at least 5 min.

The waxy grains useful in this invention may contain high levels of dietary fiber, p-glucans and antioxidants. Preferably the waxy grains contain about 14%and more total dietary fiber based on the weight of the grain and have a high tocopherol content. Preferably the whole grains contain about 6-9% soluble fiber. The total tocopherol content of the grain is preferably at least about 40 ug/g (dry weight) of unpearled grain and the A-tocopherol content in the grain is at least about 6 ug/g dry weight, preferably about 8 ug/g dry weight and more preferably about 10 ug/g dry WO 01/49132 PCT/US01/00027 0 weight. Tocopherol content may be determined using standard techniques, by C gas chromatography.

In one embodiment of this invention, the waxy grain has a P-glucan level of n about 5% to about 7% by dry weight of the grain, a total fiber content of at least about 14% by dry weight, a soluble fiber content of about 6% to about 9% by dry weight of 00 the grain and a total tocopherol content of at least about 40 ug/g dry weight, wherein the A-tocopherol content is at least about 6 ug/g by dry weight of the grain without CN a hull.

SIn one embodiment of this invention, the waxy grains are in the form of whole to grains, not subdivided during processing, and thus a product that resembles an whole grain in its natural form, is obtained. The product is storage stable and buoyant and the starch within the grain is gelatinized throughout, the grain appears translucent.

In this method the harvested, whole, waxy, grain is hydrated with heat in, a rotary cooker or a steaming screw, to increase the moisture content to about 11 to 16%. The grain is heated at 203 F (95 to about 230 F (110 for about 5 to about 15 min.

For example, the grain may be steamed for about 5 to about 15 minutes at about to about 25 psi, preferably 16-17 psi. Preferably, the grain is steamed for 7 to minutes at 16 to 17 psi. The heated grain may be left to temper at ambient temperature in a holding bin. In one embodiment, the heated grain is tempered hot, about 160 to 200 0 F (94 for 45 to 90 minutes and then bumped. More preferably, the heated grain is tempered at about 165*F (74 C) for about 1 hour. The tempered grain is then bumped lightly in a bumping mill. Preferably, the tempered grain is bumped just enough to crack the pericarp.

The heated grain, either bumped or unbumped, is then gelatinized throughout, such that it appears translucent. Gelatinization may be achieved under a variety of cooking conditions wherein the ranges oftemperature, time, pressure and moisture are varied, by using a cooker-extruder or a rotary cooker. Preferably the heated grains are cooked for about 30 minutes to about 90 minutes at about 200 0 F (94 C) to WO 01/49132 PCT/US01/00027 O about 350°F (177°C) under pressure of about 15 to 20 psi to gelatinize the starch cN throughout the grain. More preferably, the grain is cooked in a rotary cooker at 260°F S(127°C) for about 1 hour under 15-17 psi. The cooked gelatinized grains are t translucent throughout. After the grains are gelatinized throughout the grain is cooled.

The individual cooled gelatinized grains are separated and then dried to a moisture 00 content of about 18%-28%. Preferably, the gelatinized grains are dried to a moisture 00 0 content of about 18-20%. The grain is then equilibrated for about 1 hour under ambient conditions and then rolled through a roller mill to a desired thickness.

SPreferably, the thickness of the rolled grain is about 0.002 to about 0.006 inch. The S to0 grain is then dried, preferably to a moisture content of about 16-10% and then equilibrated for 24 hours. The resulting product is a storage stable, waxy grain half product that is in the form of integral grains that does not require the addition of substances to inhibit the development of rancidity. The half product may be toasted or puffed using any method that is known in the art. For example, the product may be expanded using a fluidized bed of air, or a puffing tower. The puffed or toasted product may be eaten alone or with hot or cold milk. The puffed product has pleasing organoleptic properties, including but not limited to a crisp texture. The toasted or puffed product has a moisture content of about 2.5 3% a low density and has enhanced buoyancy in addition to the enhanced crispness and storage stability, as compared to a product prepared from a non-waxy grain. The product remains buoyant in liquid, milk for at least 3 min. and preferably at least 5 min. The waxy grain may be a wholegrain, unpearled, or may be a pearled grain, prior to hydrating with heat. Preferably the waxy grain is unpearled wholegrain. Preferably the pearled grains is pearled from about 1% to about 30% of the dry weight of the waxy grain.

More preferably the grain is pearled from about 1% to about In an alternate embodiment, the gelatinized grains are prepared essentially as described supra, but rather than bumping or equilibrating at ambient temperatures and rolling the gelatinized grains that have a moisture content of 18-28%, they are mixed WO 01/49132 PCT/US01/00027 Swith another grain or soy flour or protein sources and water to form a composition which is extruded and dried to form a half product. The half product may be subsequently flaked and toasted or puffed.

Alternatively the harvested, waxy grain, whether pearled or unpearled, may be hydrated with heat in, a rotary cooker or a steaming screw, by steaming the grain 00 for about 5 to about 15 minutes, preferably about 10 minutes, at about 203 °F (95 0

C)

00 to about 230°F (1 10°C), e.g, by steaming at about 15 to about 25 psi, preferably 16- 0 17 psi. The heated grains may then be mixed with water and cooked for 30-90 minutes, preferably about 50 minutes, under about 15-25 psi, preferably 20psi. The moisture content of the grain after cooking is about 30%. The cooked grain is then dried by conventional means to a moisture content of about 18-28% preferably about 18%-20%. For example, the cooked grain is held in a tempering vessel 200F 160F for one hour.

The tempered grain is then bumped through a roller mill to a desired thickness of .030 .034 in. Thereafter, the bumped grain is dried further to a moisture content of about 10-16%. The bumped grain may be dried by conventional means, at 200°F (93 F) for about 10-20 minutes in a dryer. The dried bumped grain is then tempered for 8-12 hours at ambient temperatures. Once the product is tempered it may be further toasted or puffed by conventional means. Preferably at about 400°F (204 0 C) to about 700°F (371°C) for 15-25 sec. More preferably at about 400°F- 450°F (204-232°C) for 15-25 sec.

In a another embodiment of this invention the cooked gelatinized waxy grains are further processed into a storage stable breakfast cereal or snack, such as, e.g., flakes, shreds, puffs, nuggets, strips, or chips, which are shelf stable even without the addition of substances to inhibit the development of rancidity. In this embodiment, the waxy grains are prepared as set forth supra but instead of separating the individual cooked gelatinized grains, they are cooled and then kneaded with low shear, similar to the process used for pasta, to form dough. Preferably, the kneading is done with WO 01/49132 PCT/US01/00027 a screw and die and then put through a pasta machine, which causes slight puffing and C1 air incorporation. The dough is cooled at ambient temperatures and may be formed Sinto any suitable shape. For example, the kneaded dough may be formed into pellets then dried and puffed, or.dried and then flaked and toasted. Alternatively, the dough may be directly expanded at the die face then dried and optionally toasted.

00 In a another embodiment of this invention the steamed waxy grains may be 00 Sground into a meal of a desired consistency, a coarse or fine meal of the whole steamed grain, prior to gelatinization. The meal may be gelatinized and the

ID

0 gelatinized product then shaped into a desired shape which may be further puffed or c 10 toasted. For example the meal may be gelatinized in a cooker extruder having a die face, and then directly expanded at the die face. The meal may also be gelatinized in, a rotary cooker and the gelatinized product cooled and dried and then further processed into a storage stable product, a breakfast cereal or snack, such as, e.g., flakes, shreds, puffs, nuggets, strips, or chips, which are shelf stable even without the addition of substances to inhibit the development of rancidity.

The breakfast cereals and snacks of this invention have both an enhanced shelf life due to the storage stability of the product and an enhanced bowl life as demonstrated by the prolonged crispiness, fracturability and buoyancy in liquid. For example, the product has a bowl life of at least 3minutes and preferably at least minutes as compared to a bowl life of only 1.5 minutes for a like product prepared from a non-waxy grain.

The products of this invention may comprise one or more kinds of waxy grains and the processes may be applied to combinations of waxy grains such that two or more waxy grains are processed together to produce a mixture of processed grains..

Preferably the waxy grain has a high amounts of fiber, P-glucan and antioxidants, e.g.

tocopherols, as disclosed herein. The products of this invention may be eaten alone, mixed into a dough or the processed waxy grains of this invention may be subsequently ground to a consistency suitable for use in a dough.

WO 01/49132 PCT/US01/00027 SThe cooked, storage stable, buoyant, waxy grains of this invention may be c partially or totally covered with an edible coating, for example, with a sucrose, dextrose, an edible wax, lipid, emulsifier or protein. Suitable coatings include but itn are not limited to a whole grain rice syrup, carnauba wax, polymeric fructose, corn syrup solids, lipids, fats and oils (partially or fully hydrogenated), oo phospholipids, and emulsifiers, lecithin derived from vegetable sources such oo 0 as soybean, safflower, corn, etc., fractionated lecithins enriched in either C phosphatidyl choline or phosphatidyl ethanolamine or both, mono or diglycerides, O sodium stearoly-2-lactylate, polysorbate 80, and commercially available mono- and Slo diglycerides, saturated distilled monoglycerides and diacetyl tartaric acid esters of monoglycerides, monosodium phosphate derivatives of mono- and diglycerides of edible fats or oils, sorbitan monostearate, polyoxyethylene sorbitan monostearate, hydroxylated lecithin, lactylated fatty acid esters of glycerol and propylene glycol, polyglycerol esters of fatty acids, propylene glycol mono- and diester of fats and fatty acids, polyglycerol polyricinoleate, ammonium salts of phosphatidic acid, sucrose esters, oat extract, diacetyl tartaric acid esters of mono- and diglycerides or mixtures of these emulsifiers, proteins, gelatin, casein, caseinates, soy protein, whey protein and like products, plant resins and plant, microbial or synthetic gums, guar gum, gum arabic, locust bean gum, gum tragacanth, gum karaya and carrageenan, xanthan gum, dextran, low methoxyl pectin, propylene glycol, carboxymethyl locust bean gum and carboxymethyl guar gum and products that would improve texture and bowl life, low molecular weight fibers or carbohydrates, modified starches. The coating may be from about 5% to about by weight of the final product.

Another aspect of this invention are edible compositions that comprise the waxy grains of this invention, particularly farinaceous compositions. For example, the digestible waxy grain of this invention may be mixed with other grains and flours and may be incorporated as an additive or replacement ingredient into other food WO 01/49132 PCT/USOI/00027 0 products such as, R-T-E cereals, Special K T M Total

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or Product 19

TM,

Muesli, granola grain clusters, snack bars, biscuits, crackers, bread, cakes, muffins, Sand pie crusts. The waxy grains of this invention may also be incorporated into tIt candies, chocolate bars.

Additional ingredients may be added to the processed waxy grain prior to, 00 during or after cooking. For example, natural or artificial sweeteners, spices, salts or flavorings may be added. Examples of sweeteners that are suitable for use in this C invention include, but are not limited to dextrose, rice syrup, corn syrup, sucrose, glucose or fructose oligosaccharides. Suitable spices include but are not limited to nutmeg, cloves, cinnamon, and allspice. Suitable flavorings include but are not limited to vanilla, a fruit extract, orange, lemon, strawberry, cherry, blueberry, or pineapple, and cocoa.

The methods disclosed herein are also applicable to pearled waxy grains.

Pearling removes various proportions of the bran from the outer layers ofwhole grain.

For example, a small amount of the bran may be removed, accounting for a loss of only about 1% of the dry weight of the grain, or essentially all the bran may be removed producing a white grain with essentially no brown color from the bran layer.

Pearled grains produce a product that is preferred by some consumers. The grain may be pearled by any suitable method and preferably the pearled grain is pearled from about 1% to about 30% of the weight of the grain, more preferably about 1 to about The methods of this invention produce a digestible, storage stable food product from pearled waxy grain but the fiber and P-glucan levels may be reduced as compared to the non-pearled waxy grain due to the loss of the outer layers of the grain. Even though the fiber and p-glucan levels of these products may be reduced by the pearling, the product still retains its enhanced storage stability, without the addition of preservatives that inhibit rancidity, as evidenced by the reduced rate at which rancid odors and tastes are produced and the slow change in moisture content leading to an alteration in appearance, odor, taste and texture "staleness" after WO 01/49132 PCr/UJS01/00027 extended storage in an air tight or a conventional cereal container having a lining.

-N Preferably, the product is stable for at least 6 months, more preferably 12 months without the addition of preservatives with inhibit the development of rancidity, and I. the processed waxy grain product maintains pleasing organoleptic properties, a fresh taste and a crisp texture.

oo The processed waxy grains ofthis invention have textures that are significantly 00 different than processed non-waxy grains having significantly less surface roughness and significantly enhanced buoyancy and crispness as compared to non-waxy Sproducts. The processed waxy grains do not become rancid even without the addition c lo of preservatives, as determined by taste, texture or smell or by a measure of the hexanal content in the head space of the packaged waxy grain or the level ofhexanal in the waxy grain itself. Those of skill in the art appreciate that the levels ofhexanal that are considered acceptable depend on the type of grain and can be readily determined, by gas chromatography, see Feneley, Accelerated Shelf-Life Testing of a Ready to Eat Cereal, Masters Thesis, Dept. of food Science and Human Nutrition, Michigan State University (1998); Fritsch and Gale, "Hexanal as a measure of rancidity in low fat foods", J. Amer. Oil Chem. Soc. 54:225 (1976), incorporated herein by reference, for a discussion on hexanal content and its relationship to rancidity.

The following examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention described herein.

WO 01/49132 PCT/US01/00027 U EXAMPLE 1 Hulless, waxy barley were received cleaned from the supplier with less than 1% residual hull attached. The barley was steamed in a rotary cooker for 7-10 minutes at 17 psi and then tempered at 165°F (74 C) for 1 hour prior to bumping.

The tempered barley was lightly bumped through a roller mill, just enough to 00 crack the pericarp of the grain. The bumped barley was then added back to the rotary 00 cooker and steamed 10 15 minutes at 17 psi (260 0 F, 127°C). The cooker was depressurized and a mixture of sugar, salt, high fructose maize syrup, was then added.

0 The cooker was then pressurized to 17 psi for approximately 30 to 40 minutes to c 10io gelatinize the starch throughout the grain. The barley was then cooled and individual grains were separated. The moisture content was about 30 33%. The individual grains were then dried for 20 minutes at 200 0 F (94 C) to a moisture range of 20 18%. The product was then equilibrated for I hour at ambient air. The equilibrated barley was then rolled through a roller mill to form elongated thin berries approximately 0.004 inch thickness. The berries were then dried down to 14-12% moisture and then equilibrated for 24 hours. The dried equilibrated product was then expanded using a fluidized bed of air at 375F (190°C) for 25 seconds. The moisture content of the expanded product was about 2.5-3%.

EXAMPLE 2 The grain was processed as described in Example 1 until the drying step wherein the individual gelatinized grains were dried to a moisture content of 20% to 18%. The individual grains were mixed with a soy flour to about 25% of the total weight, and the mix of grain and flour were added to a pasta press and blended with water, about 10% of the total weight. The resulting product was extruded as a pellet using a press. The pellets were then dried to 16% moisture and flaked through a roller mill. The flakes were then toasted in a fluidized bed of air using the same procedure WO 01/49132 PCT/US01/00027 Sand temperatures as set forth in Example 1. The moisture content of toasted product 0 was about 2.5 to 3%.

in EXAMPLE 3 Waxy Hulless Barley CDC Candle 20.00 lbs.

oo Sugar 3.43 lbs.

00 Salt .37 lbs.

CI High fructose corn syrup .70 lbs.

Water 3.74 lbs.

Pre-Processing Procedure: The waxy barley was washed and steeped in warm (120°F, 49 0 C) water for minutes and then put on a screen and drained. The barley was put in a large barrel and steamed using a live steam hose for 5 minutes. The product was left in a bucket to temper atl60F-200°F (71°C-93°C) for 1 hour to increase the moisture content and loosen the pericarp. The product was then bumped, similarly to an old fashion-rolled oat, through a small scale flaking mill. Fifty pounds of the bumped product was produced.

Cooking procedure: A cooker was loaded with 20 pounds of the pre-processed barley. The barley was cooked for about 15 minutes by sealing the cooker and increasing the pressure at a rate sufficient to reach 16 psi in 9 minutes and then cooked for the remaining time with 16 psi steam (260°F, 127°C). The pressure was released and flavor was added through an injection point and the flavors and barley were mixed for 5 minutes. The pressure was then put back on the cooker. The product was then cooked for minutes at 16 psi (260°F, 127°C).

WO 01/49132 PCT/US01/00027 0 The cooked waxy barley product was deposited into a tub and then air-cooled.

C The product was pulled apart into quarter size pieces. The quarter sized pieces were then sized through a pellet mill. The pellets were cooled and then air-dried for tn minutes. The dried pellets were then flaked to 1 V 2 cm to 2 cm in size. The flakes were dried at 190 0 F for 15 minutes to 12-14% moisture. The dried flakes were toasted 00 at 400OF for about 25 seconds, which expanded the flakes to 3.5cm to 4 cm in length and 2 cm to 3 cm in width. The thickness was 0.66 0.76 mm and the cross flake C thickness was 0.094 0.116 mm. The flakes were robust light and airy. The product Sfloated and did not become soggy for at least 3 minutes in milk.

EXAMPLE 4 Dry Ingredients Whole Grain Waxy Barley Meal 120.00 Kg Sucrose 9.00 Kg Salt 2.26 Kg Corn oil .53 Kg Sodium Bicarbonate .53 Kg Liquid Premix Malt extract .547 Kg HFCS/42 DE Corn Syrup/water 6.08 Kg Liquid Premix Ratio To Dry Ingredients 5.00% The waxy barley was steamed and then held at 200 160°F (93 °C-71 °C) for 1 hour for lipase deactivation. The waxy whole grain was the ground into a stable meal. The ground waxy barley was mixed with the remaining dry ingredients set forth above. The dry ingredients were mixed in a twin screw extruder and the liquid ingredients were injected into the mixed dry ingredients, mixed and the mixture was extruded in the form of a tubular dough. The temperature of the dough out of the extruder was about 127-130 oC (286-291 The dough was then cooled and formed WO 01/49132 PCT/USOI/00027 into pellets containing 20 25% moisture. The pellets were then sheeted and formed N and dried to 10- 12% moisture for 20 min at 60-70 0 C (165-183 0 The productwas then puffed at about 400 F (204 C) 25 sec.

In an alternate embodiment, after the dry and liquid ingredients were mixed in 00 a twin screw extruder, the mixture was then directed expanded from the die at an exit 00 moisture of 6-9% and the product was then dried to 3%.

SEXAMPLE To assay storage stability, the sensory attributes, aroma, taste and texture of waxy barley flakes prepared as described in Example 1 were evaluated by a professional cereal stability panels at 3, 6, 9 and 12 weeks of storage under hot room conditions wherein the temperature is 100 F (37.8 and the humidity is 70%, and at 2, 4, 6, 8, 10 and 12 months of storage under at 70 °F (21 35 relative humidity. The samples were also assayed for changes in moisture and water activity and for oxidative stability. The results are displayed in Tables 1 and 2, Figures 3A and 3B, and Figures 4A and 4B. Analysis of the time trend data was conducted using linear regression over time.

Sensory Attributes after storage The waxy barley flakes did not develop a cardboard aroma, a musty, stale woody aromatic associated with wet cardboard, or a painty off taste, similar to linseed oil or oil-based paint, associated with oxidized oil, which are typical of rancid products, during the 12 week or 12 month storage.

Chemical Analysis Chemical analyses of the water activity and moisture content of the waxy barley flakes indicated that the moisture and water activity increased slightly over time. When stored at 70 0 F (21 35 relative humidity, the water activity increased by about 0.05% per month (Figure 3A) and the water activity increased by WO 01/49132 PCT/US01/00027 O about 0.009 per month (Figure 3B). When stored under hot room conditions the water N activity increased by about 0.5% per month (Figure 4A) and the water activity increased by about 0.003 per month (Figure 4B). Although the increases in the moisture and water activity were significantly different, they were low.

00 00

CIA

0', WO 01/49132 WO 0149132PCT/US01/00027 Table 1: Sensory Attributes Hot Room (100 0 F, 37.70 C, 35% 111) Attributes Initial 3 Weeks 6 Weeks 9 Weeks 12 Weeks Cardboard 0.0 0.0 0.3 0.4 0.2 Aroma Painty 0.0 0.0 0.0 0.0 0.1 Aroma Cardboard 0.0 0.0 0.1 0.3 0.2 Flavor Painty 0.0 0.0 0.0 0.0 0.0 Flavor Hardness 8.0 6.5 7.5 7.6 7.7 Crispness 8.9 9.0 9.0 8.9 8.6 =Slight; 6-1 O=Moderate; 11I- 15 =Strong Table 2: Sensory Attributes Room Temperature (70 0 F, 21.1 0 C, 35% RH) Attributes Initial 2 mos. 4 mos. 6 mos. 8 mos. 10 mos. 12 mos.

Cardboard 0.0 0.3 0.3 0.2 0.0 0.3 0.3 Aroma Painty 0.0 0.0 0.0 0.0 0.0 0.0 0.1 Aroma Cardboard 0.0 0.0 0.3 0.1 0.3 0.1 0.2 Flavor Painty 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Flavor Hardness 8.0 7.4 7.9 7.7 7.8 8.0 7.7 Crispness -18.9 9.0 8.8 8.6 8.6 8.4 19.1, Slight; 6-1 0=Moderate; 11-15 Strong 00 -24- O To assay for oxidative stability, the hexanal levels in the headspace of Q the test product were assayed. The hexanal levels remained low in the product C) throughout the test. A rapid increase in the accumulation of hexanal, known as the time of break point that is associated with consumers detecting rancidity, was not observed.

00 In the claims which follow and'in the preceding description of the 0o O invention, except where the context requires otherwise due to express Slanguage or necessary implication, the word "comprise" or variations such as N "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

N MelboumelCoseskPatent7OOO47999 P47875AU 1kSpeos\P47875AU.1 First Amendments.doc

Claims (39)

1. 2. Process of claim 1, wherein the waxy grain is a waxy oat or a waxy barley.
2. 3. Process of claim 1 or claim 2, where said waxy grain in step is tempered for about 1 hour to about 2 hour at about 1600 F (71 C) to about 2000 F (930 C).
3. 4. Process of claim 1 or claim 2, wherein said tempering of the heated waxy grain in step is about 1 hour at ambient temperature. Process of claim 1 or claim 2, wherein said tempering of the heated waxy grain in step is about 1 hour at about 260°F (1270C).
4. 6. Process of any one of claims 1 to 5, wherein the tempered waxy grain is heated in step for about 45 minutes to about 90 minutes at 200°F (93°C) to about 350°F (177 0 C). N:\Melboume\Cases\Patent47000-47999\P47875 AU 1\Specis\P47875.AU 1 First Amendmentsdoc 00 -26- 0 0 7. Process of any one of claims 1 to 6, further comprising separating the Q cooled waxy grain of step into separate kernels.
5. 8. Process of claim 7, further comprising toasting the separate kernels. 00 9. Process of claim 7, further comprising drying the separate kernels to a 00 0 moisture content of about 10% to about 16% then heating the dried kernels to 0 about 400TF (204°C) to about 700°F (371 C) to puff the kernels. O
6. 10. Process of any one of claims 1 to 6, further comprising kneading the gelatinized, dried and cooled waxy grain under low shear to form a dough.
7. 11. Process of any one of claims 1 to 6, further comprising toasting or puffing the cooled and dried waxy grain of step
8. 12. Process of any one of claims 1 to 11, wherein the waxy grain is pearled prior to step
9. 13. Process of any one of claims 1 to 12, wherein the waxy grain prior to heating has high lipase and peroxidase levels.
10. 14. Process for preparing a cooked, buoyant, storage stable, waxy barley comprising: hydrating the waxy barley having no more than 10% amylose to a moisture level of from 11 to 16% and then heating the waxy barley for about to about 15 minutes at about 203 0 F (95 0 C) to about 230°F (110°C) with moisture to inactivate the lipases and peroxidases then tempering the waxy barley for about 1 hour to 2 hours; further cooking the tempered waxy barley to fully gelatinize it throughout; and cooling and drying the waxy barley, N:\Melboume\Cases\Patent7000-47999\P47875 AU. \Speas\P47875AU.1 First Amendments doc 00 -27- O O wherein said waxy barley is storage stable for at least about six months without Q additives that inhibit development of rancidity.
11. 15. Process of claim 14, wherein the waxy barley is a hulless waxy barley. 00 16. Process of claim 15, wherein the barley is selected from the group O O consisting of CDC Candle, Merlin, HB803, and prowashapawana.
12. 17. Process of any one of claims 14 to 16, wherein the barley has a P-glucan level of about 5% to about 7% by weight of the waxy grain.
13. 18. Process of any one of claims 14 to 17, wherein the waxy barley has a soluble fiber content of about 6% to about 9% by weight of the waxy barley.
14. 19. Process of any one of claims 14 to 18, further comprising kneading the gelatinized, dried and cooled waxy barley under low shear to form a dough. Process of claim 19, further comprising shaping and drying the dough to a moisture content of about 10% to 16%.
15. 21. Process of claim 20, further comprising toasting or puffing the dried shaped dough.
16. 22. Process of claim 20, wherein the dried shaped dough is puffed by heating the dried shaped dough to about 3800 F (1930 C) to about 700°F (371 C).
17. 23. Process of any one of claims 14 to 22, wherein the waxy barley is pearled.
18. 24. Process of claim 23, wherein the waxy barley is pearled from about 1% to about 20% by weight of the barley. N:\Melboume\Cases\Patent\47000-47999P47875 AU1\Speds\P47875.AU.1 First Amendments.doc 00 -28- 0 Cooked, buoyant, storage stable, fully gelatinized waxy grain produced cr) by the process of any one of claims 1 to 13 or claims 27 to 47.
19. 26. Cooked, buoyant, storage stable, fully gelatinized waxy barley produced oo by the process of any one of claims 14 to 24 or claims 48 to 56. oo S27. Process of claim 10, wherein the dough is shaped and dried. IND
20. 28. Process of claim 27, further comprising drying the dough to a moisture content of about 10% to 16%.
21. 29. Process of claim 27 or claim 28, wherein the shaped and dried dough is toasted or puffed. Process of claim 27 or claim 28, wherein the dried shaped dough is puffed by heating the dried shaped dough to about 380°F (193 0 C) to about 700°F (371°C).
22. 31. Process of any one of claims 1 to 6, wherein the grain of step is milled after heating and prior to gelatinizing to produce a ground meal.
23. 32. Process of claim 31, further comprising shaping the gelatinized ground meal and drying the shaped gelatinized ground meal to a moisture content of about 10% to 16%.
24. 33. Process of claim 31, wherein the ground meal is gelatinized in a cooker- extruder or a rotary cooker. 3o 34. Process of claim 33, further comprising extruding the gelatinized ground meal into a product having a desired shape. N:\Melboume\Cases\Patentl7000-47999\P47875 AU.\Specis\P47875AU 1 First Amendments. oc 00 -29- 0 0 35. Process of claim 34, further comprising toasting or puffing the shaped Q product. 0 36. Process of claim 35, wherein the dried shaped gelatinized milled waxy grain is puffed by heating to about 380°F (193°C) to about 700°F (371 C). 00 00 oo 0 37. Process of claim 31, wherein the ground meal is gelatinized in a cooker- O extruder and directly expanded. IND
25. 38. Process of any one of claims 1 to 6, further comprising milling the gelatinized, dried and cooled waxy grain of step to produce a ground meal.
26. 39. Process of claim 38, wherein said ground meal is further processed into a product having a desired shape. Process of claim 39, wherein said shape is a flake, shred, puff, nugget, strip or chip.
27. 41. Process of claim 39 or claim 40, wherein the shaped product is toasted or puffed.
28. 42. Process of claim 39, wherein the shaped product is dried to a moisture content of about 10% to 16%.
29. 43. Process of claim 42, further comprising toasting or puffing the dried shaped product.
30. 44. Process of any one of claims 1 to 6, wherein the gelatinized cooled and dried grain in step is bumped, flaked, puffed or toasted. Process of any one of claims 1 to 6, wherein the waxy grain in step is gelatinized in a cooker-extruder having a die face or a rotary cooker. NWeibou asesPaen470 7999 AU SpcisP47875AU.1 First Amendmentsdoc 00 0
31. 46. Process of claim 45, wherein the gelatinized waxy grain in step is r) extruded, prior to cooling and drying, and is directly expanded at the die face.
32. 47. Process of claim 46, wherein the directly expanded gelatinized grain is oo subsequently toasted. 00 S48. Process of claim 14 to 18, wherein the waxy barley of step is milled ND after heating and prior to gelatinizing to produce a ground meal.
33. 49. Process of claim 48, further comprising shaping the gelatinized ground meal and drying the shaped gelatinized meal to a moisture content of about to 16%.
34. 50. Process of claim 48 or claim 49, wherein the ground meal is gelatinized in a cooker-extruder or a rotary cooker.
35. 51. Process of claim 48 or claim 49, wherein the ground meal is gelatinized in a cooker-extruder and directly extruded.
36. 52. Process of any one of claims 14 to 18, further comprising milling the gelatinized waxy barley of step to produce a ground meal.
37. 53. Process of claim 52, wherein said ground meal is further processed into a product having a desired shape.
38. 54. Process of claim 53, wherein said shape is a flake, shred, puff, nugget, strip or chip.
39. 55. Process of any one of claims 14 to 18, wherein the gelatinized barley in step is bumped, flaked, puffed or toasted. N:\Melboume\Cases\PatentW7000-47999\P47875.AU 1Specis\P47875.AU 1 First Amendments doc S-31- 0 0 56. Process for preparing a cooked, buoyant, storage stable, waxy barley Ssubstantially as herein described with reference to any one of Examples 1 to and/or Figures 1 to 4B thereof. 00 00 O0 N \Melboume\Cases\Patent\47000-47999\P47875.AU.1\Speis\P47875 AU1 First Amendments.doc